Synthesis, Crystal Structure and Catalytic Performance of Zinc Complex Containing 2-(Aminomethyl)pyridine Ligand†

doi:10.7503/cjcu20131290

Abstract

Abstract:

A novel zinc metal complex [Zn( AMPy)₂(OAc)]₂[Zn(OAc)₄] [AMPy=2-(aminomethyl)pyridine] was synthesized by the reaction of zinc acetate to 2-(aminomethyl)pyridine ligand. The structure of the complex was characterized by ¹H NMR, IR, elemental analysis and X-ray single crystal diffraction. The crystal structural analyses show that the complex belongs to triclinic system, space group is P $1 ¯$ with a=1.07360(19) nm, b=1.2491(2) nm, c=1.8976(3) nm, α=83.809(2)°, β=89.595(2)°, γ=65.708(2)°, V=2.3039(7) nm³, Z=2. The complex molecular consists of three different coordinated zinc ions which are connected by intramolecular hydrogen bonds into a total molecular, and 2D network structure is further formed by intermolecular hydrogen bonds. The catalytic performance of the metal complex in Henry reaction was studied, and the optimum catalytic conditions were obtained. The results show that the complex exhibits a high catalytic performance with 9%(molar fraction) of catalyst loading, methanol as solvent and reaction at room temperature for 20 h.

Key words: 2-(Aminomethyl)pyridine, Zinc acetate, Complex, Crystal structure, Catalytic performance

CLC Number:

O614
O643

TrendMD:

LIU Chao, ZHUO Xin, ZHANG Hu, LIU Xinhua. Synthesis, Crystal Structure and Catalytic Performance of Zinc Complex Containing 2-(Aminomethyl)pyridine Ligand^†[J]. Chem. J. Chinese Universities, 2014, 35(5): 928.

Figures/Tables 8

Table 1 Crystallographic data for the complex

Empirical formula	C₃₆H₅₀N₈O₁₂Zn₃	Z	2
Formula weight	982.95	D_c/(g·cm^-3)	1.405
Crystal system	Triclinic	μ/mm^-1	1.612
Space group	P $1 ˉ$	F(000)	1000
Temperature/K	296(2)	Crystal size	0.35 mm×0.32 mm×0.27 mm
a/nm	1.07360(19)	θ range for data collection/(°)	1.08—26.00
b/nm	1.2491(2)	Reflections collected/unique, R_int	17256/8719, 0.0809
c/nm	1.8976(3)	Data/restraints/parameters	8719/0/532
α/(°)	83.809(2)	Goodness-of-fit on F²	1.002
β/(°)	89.595(2)	Final R indices [I>2σ(I)]	R₁=0.0694, wR₂=0.1758
γ/(°)	65.708(2)	R indices(all data)	R₁=0.1965, wR₂=0.2323
V/nm³	2.3039(7)

Table 1 Crystallographic data for the complex

Empirical formula	C₃₆H₅₀N₈O₁₂Zn₃	Z	2
Formula weight	982.95	D_c/(g·cm^-3)	1.405
Crystal system	Triclinic	μ/mm^-1	1.612
Space group	P $1 ˉ$	F(000)	1000
Temperature/K	296(2)	Crystal size	0.35 mm×0.32 mm×0.27 mm
a/nm	1.07360(19)	θ range for data collection/(°)	1.08—26.00
b/nm	1.2491(2)	Reflections collected/unique, R_int	17256/8719, 0.0809
c/nm	1.8976(3)	Data/restraints/parameters	8719/0/532
α/(°)	83.809(2)	Goodness-of-fit on F²	1.002
β/(°)	89.595(2)	Final R indices [I>2σ(I)]	R₁=0.0694, wR₂=0.1758
γ/(°)	65.708(2)	R indices(all data)	R₁=0.1965, wR₂=0.2323
V/nm³	2.3039(7)

Table 2 1H NMR(CDCl3, δH) and 13C NMR(CDCl3, δC) data of the products

Product	δ
1	δ_H: 7.39—7.34(m, 5H, Ar—H), 5.46—5.41(m, 1H, CH), 4.62—4.45(m, 2H, CH₂), 3.01(br, 1H, OH). δ_C: 138.1, 128.7, 128.5, 125.9, 81.1, 70.7
2	δ_H: 7.23—7.11(m, 4H, Ar—H), 5.46—5.40(m, 1H, CH), 4.64—4.46(m, 2H, CH₂), 2.74(br, 1H, OH), 2.34(s, 3H, CH₃). δ_C: 138.6, 134.9, 129.4, 125.6, 80.9, 70.6, 20.9
3	δ_H: 7.46 —7.15(m, 4H, Ar—H), 5.70(m, 1H, CH), 4.48—4.39(m, 2H, CH₂), 2.88(br, 1H, OH), 2.33(s, 3H, CH₃). δ_C: 136.2, 134.4, 130.9, 128.7, 126.8, 125.7, 80.3, 68.0, 21.2
4	δ_H: 7.29(d, J=8.6 Hz, 2H, Ar—H), 6.86(d, J=8.6 Hz, 2H, Ar—H), 5.36—5.32(m, 1H, CH), 4.57—4.36(m, 2H, CH₂), 3.74(s, 3H, CH₃), 2.72(br, 1H,OH). δ_C: 159.6, 130.0, 126.9, 114.0, 80.9, 70.3, 55.0
5	δ_H: 7.40—7.21(m, 4H, Ar—H), 5.59—5.54(m, 1H, CH), 4.65—4.56(m, 2H, CH₂), 3.84(s, 3H, OCH₃), 3.17(br, 1H, OH). δ_C: 155.8, 129.7, 127.0, 125.9, 121.0, 110.4, 79.8, 67.6, 55.3
6	δ_H: 8.29(d, J=8.7 Hz, 2H, Ar—H ), 7.64(d, J=8.7 Hz, 2H, Ar—H ), 5.62—5.60(m, 1H, CH), 4.63—4.54(m, 2H, CH₂), 3.16(br, 1H, OH). δ_C: 147.7, 144.7, 126.6, 123.9, 80.3, 69.6
7	δ_H: 8.05(d, J=8.1 Hz, 1H, Ar—H), 7.93(d, J=7.7 Hz, 1H, Ar—H), 7.73(m, 1H, Ar—H), 7.53(m, 1H, Ar—H), 6.02—5.99(m, 1H, CH), 4.77—4.54(m, 2H, CH₂), 3.21(br, 1H, OH). δ_C: 147.5, 135.0, 134.8, 130.0, 129.2, 125.4, 80.7, 67.3
8	δ_H: 7.58—7.55(d, J=8.3 Hz, 2H, Ar—H ), 7.31—7.29(d, J=8.3 Hz, 2H, Ar—H), 5.46—5.44(m, 1H, CH), 4.60—4.48(m, 2H, CH₂), 2.94(br, 1H, OH). δ_C: 136.8, 131.8, 127.3, 122.6, 80.6, 70.0
9	δ_H: 7.60(d, J=7.5 Hz, 1H, Ar—H), 7.45(d, J=8.0 Hz, 1H, Ar—H), 7.34—7.19(m, 2H, Ar—H), 5.78—5.73(m, 1H, CH), 4.63—4.47(m, 2H, CH₂), 3.22(br, 1H, OH). δ_C: 136.8, 132.7, 130.0, 127.9, 127.7, 121.5, 79.6, 70.1

Table 3 Selected bond lengths(nm) and bond angles(°) of the complex

Zn1—O6	0.1980(6)	Zn1—O7	0.1956(6)	Zn1—O8	0.1962(6)
Zn1—O9	0.1980(6)	Zn2—N4	0.2080(7)	Zn2—N1	0.2085(7)
Zn2—N3	0.2138(8)	Zn2—O1	0.2165(7)	Zn2—N2	0.2193(7)
Zn2—O2	0.2302(6)	Zn3—N8	0.2067(7)	Zn3—N5	0.2079(8)
Zn3—N6	0.2140(9)	Zn3—N7	0.2145(8)	Zn3—O4	0.2229(7)
Zn3—O3	0.2260(7)
O7—Zn1—O8	116.5(3)	O7—Zn1—O6	113.9(3)	O8—Zn1—O6	99.8(3)
O7—Zn1—O9	97.0(3)	O8—Zn1—O9	114.4(3)	O6—Zn1—O9	116.3(3)
N4—Zn2—N1	111.0(3)	N4—Zn2—O1	105.5(3)	N3—Zn2—N2	176.3(3)
N1—Zn2—O2	88.0(3)	O1—Zn2—O2	57.7(2)	N8—Zn3—N5	105.3(3)
N6—Zn3—N7	167.5(4)	N5—Zn3—O4	106.1(3)	N8—Zn3—O3	93.2(3)
O4—Zn3—O3	58.2(2)

Fig.1 Molecular structure of the complex with thermal ellipsoids at 30% probability level

Fig.2 2D network structure of the complex via hydrogen bonds^Symmetry code: #1: x, -1+y, z; #2: 2-x, -y, 1-z; #3: 2-x, 1-y, -z; #4: x, 1+y, z. H atoms except amino are omitted for clarity.

Table 4 Hydrogen bonds of the complex*

D—H…A	d(D—H)/nm	d(H…A)/nm	d(D…A)/nm	∠(DHA)/(°)
N1—H1B…O6	0.0900	0.2360	0.3095	139.00
N1— H1C…O3#1	0.0900	0.2180	0.3008	152.00
N4—H4B…O8	0.0900	0.2110	0.2998	167.00
N4—H4C…O10#2	0.0900	0.2080	0.2941	161.00
N5—H5B…O9	0.0900	0.2100	0.2961	160.00
N5—H5C…O4#3	0.0900	0.2050	0.2953	176.00
N8—H8B…O7	0.0900	0.2090	0.2975	166.00
N8—H8C…O2#4	0.0900	0.2010	0.2870	161.00

Table 5 Optimization of the reaction conditions of nitromethane to benzaldehyde

Entry	Catalyst loading (molar fraction, %)	Solvent	Time/h	Yield(%)	Entry	Catalyst loading (molar fraction, %)	Solvent	Time/h	Yield(%)
1	3	Methanol	20	21.0	8	9	Methanol	15	68.0
2	6	Methanol	20	51.5	9	9	Methanol	25	83.5
3	9	Methanol	20	83.5	10	9	THF	20	80.5
4	12	Methanol	20	84.5	11	9	CH₂Cl₂	20	71.0
5	15	Methanol	20	84.0	12	9	Et₂O	20	77.5
6	9	Methanol	5	0	13	9	Zn(OAc)₂	20	15
7	9	Methanol	10	15.0	14	9	AMPy	20	0

Table 6 Catalytic reactions of nitromethane to different aromatic aldehydes

Entry	Substrate	Yield(%)	Entry	Substrate	Yield(%)
1	C₆H₅CHO	83.5	6	p-NO₂C₆H₄CHO	90.5
2	p-CH₃C₆H₄CHO	79.0	7	o-NO₂C₆H₄CHO	87.5
3	o-CH₃C₆H₄CHO	72.5	8	p-BrC₆H₄CHO	85.0
4	p-MeOC₆H₄CHO	69.0	9	o-BrC₆H₄CHO	86.5
5	o-MeOC₆H₄CHO	59.0

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